The Library
Data for Assessing and rationalizing the performance of Hessian update schemes for reaction path Hamiltonian rate calculations
Tools
Chantreau Majerus, Raphael, Robertson, Christopher and Habershon, Scott (2022) Data for Assessing and rationalizing the performance of Hessian update schemes for reaction path Hamiltonian rate calculations. [Dataset]
Plain Text (Readme file)
README.txt  Published Version Available under License Creative Commons Attribution 4.0. Download (3364b) 

Archive (ZIP) (Dataset)
update_hessian_paper_data_final.zip  Published Version Available under License Creative Commons Attribution 4.0. Download (249Kb) 
Official URL: http://wrap.warwick.ac.uk/155731/
Abstract
The reaction path Hamiltonian (RPH) can be used to calculate chemical reaction rate constants, going beyond transitionstate theory in taking account of recrossing by providing an approximation to the dynamic transmission coefficient. However, the RPH necessitates the calculation of the Hessian matrix at a number of points along the input minimum energy path; the associated computational cost stands as a bottleneck in RPH calculations, especially if one is interested in using highaccuracy electronic structure methods. In this work, three different Hessian update schemes (symmetric rank1, Powellsymmetric Broyden, and Bofill updates) are assessed to see whether or not they reliably reproduce calculated transmission coefficients for three different chemical reactions. The symmetric rank1 scheme and the Powellsymmetric Broyden scheme both resulted in the most reliable and accurate Hessian update methods, with transmission coefficients which were in good agreement with those calculated by the standard RPH calculations using analytical Hessian matrices. The relative accuracy of the different Hessian update schemes is further rationalized by investigating the approximated coriolis and curvature coupling terms along the reactionpath, providing insight into when these schemes woould be expected to work well. Furthermore, the associated computational cost associated with the RPH calculations was substantially reduced by the tested update schemes. Together, these results provide useful rulesofthumb for using Hessian update schemes in RPH simulations.
Item Type:  Dataset  

Subjects:  Q Science > QC Physics Q Science > QD Chemistry 

Divisions:  Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Chemistry > Computational and Theoretical Chemistry Centre 

Type of Data:  ASCII text files  
Library of Congress Subject Headings (LCSH):  Chemical kinetics  Mathematical models, Chemical reactions  Mathematical models, Molecular theory, Chemistry, Physical and theoretical  Data processing, Statistical mechanics  
Publisher:  University of Warwick, Department of Chemistry  
Official Date:  2 February 2022  
Dates: 


Status:  Not Peer Reviewed  
Publication Status:  Published  
Media of Output (format):  .dat  
Access rights to Published version:  Open Access  
Copyright Holders:  University of Warwick  
Description:  Figure_2_a.dat contains the data for Figure 2 

RIOXX Funder/Project Grant: 


Related URLs:  
Contributors: 

Request changes or add full text files to a record
Repository staff actions (login required)
View Item 
Downloads
Downloads per month over past year